CN104837626A - Resin film and resin film laminated ornamental panel - Google Patents

Resin film and resin film laminated ornamental panel Download PDF

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Publication number
CN104837626A
CN104837626A CN201380063169.5A CN201380063169A CN104837626A CN 104837626 A CN104837626 A CN 104837626A CN 201380063169 A CN201380063169 A CN 201380063169A CN 104837626 A CN104837626 A CN 104837626A
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CN
China
Prior art keywords
layer
resin
terephthalate resin
plant
polybutylene terephthalate
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Granted
Application number
CN201380063169.5A
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Chinese (zh)
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CN104837626B (en
Inventor
岩下宽之
河村悟史
逸见勇介
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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Publication of CN104837626A publication Critical patent/CN104837626A/en
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Publication of CN104837626B publication Critical patent/CN104837626B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin film using plant-derived raw material as much as possible, and an ornamental panel in which the resin film is laminated on a base panel. A resin film characterized by including at least one of the plant-derived resin layers (A, B, or C) described below. A layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a blended composition of two or more of these resins. B layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a product obtained by adding a plant-derived compatibilizer and/or a plant-derived elastomer to a blended composition of two or more of these resins. C layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a product obtained by adding a plant-derived ionomer to a blended composition of two or more of these resins.

Description

Resin molding, with resin molding composite decorating board
Technical field
The invention relates to a kind of resin molding and the resin molding composite decorating board that comprise the raw material deriving from plant, especially about a kind of as much as possible reduce petroleum use on earth environment impact less resin molding and on substrate this resin molding of compound and resin molding composite decorating board.
Background technology
Previously, as the membrane material be widely used in decorative panel, packaging material, container etc., widely use PET, polyethylene, polypropylene etc.These materials be use oil etc. limited resource as raw material, therefore worry the exhaustion of these materials.And then, the resources such as this oil go through the material that very long history makes tellurian carbon fixation, when discard the resin obtained by these materials, burning etc. processes, can great amount of carbon dioxide be produced, worry the deterioration of the earth environment caused by the increase of carbon dioxide, warmization.
In addition, as by the membrane material obtained for the purpose of biomarker, proposition has the membrane material using PLA (polylactate, PLA) as raw material (with reference to patent document 1,2) or comprises the polyolefinic decorating film (with reference to patent document 3) using and derive from the raw material of plant.As the membrane material using these to derive from the raw material of plant, exploitation has multiple material, also can relatively easily obtain, and carries out the absorption of carbon dioxide, fixes in its generative process, with regard to aspect with regard to reusable edible or the aspect for non-exhausted resource, be better than petroleum resource.
Look-ahead technique document
Patent document
Patent document 1 Japanese Patent Laid-Open 2008-73998 publication (PLA)
Patent document 2 Japanese Patent Laid-Open 2008-207535 publication (PLA)
Patent document 3 Japanese Patent Laid-Open 2010-36341 publication (polyolefin decorating film)
Summary of the invention
But the use disclosed about patent document 1 ~ 3 derives from the membrane material of the raw material of plant, does not think that the physical property of decorative panel compound film is abundant.Such as, form multicoat membrane in composite single layer film or in order to be compound in the situation on substrate for ornament materials time, there are adhesion, processability, durability or anti-flammability etc. for film oneself requirement, but do not think that the previous membrane material deriving from plant has sufficient characteristic.
The object of the present invention is to provide a kind of use as much as possible derive from plant raw material, the deterioration of earth environment or the use amount of limited resources can be reduced and for high-quality resin molding and use its decorative panel.Another object of the present invention is to provide a kind of above-mentioned resin molding of compound on the substrates such as metallic plate and the decorative panel of adhesion or excellent in workability.In addition, of the present invention and then another object is to provide a kind of use to derive from the resin molding of the raw material of plant, and it is to meet the biotic ratio of the mode boosted tree adipose membrane of the condition of biomarker and to give and the previous performance utilizing the resin molding same degree of petroleum plastic cement.
(1) resin molding of the 1st embodiment of the present invention comprises the following resin bed (A, B or C layer) deriving from plant of more than 1 layer:
A layer: polytrimethylene terephthalate (the polytrimethylene terephtalate deriving from plant, PTT) resin, derive from PET (the polyethylene terephthalate of plant, PET) resin, derive from the olefin-based resin (polypropylene (polypropylene of plant, PP), polyethylene (polyethylene, PE)), derive from Merlon (polycarbonate, the PC) resin of plant arbitrary in or these blend compositions of more than two kinds above-mentioned;
B layer: in derive from plant polytrimethylene terephthalate (PTT) resin, derive from plant PET (PET) resin, derive from plant olefin-based resin (polypropylene (PP), polyethylene (PE)), derive from plant Merlon (PC) resin any one or these blend compositions of more than two kinds above-mentioned in add and derive from the compatilizer of plant and/or derive from the elastomer of plant;
C layer: in derive from plant polytrimethylene terephthalate (PTT) resin, derive from plant PET (PET) resin, derive from plant olefin-based resin (polypropylene (PP), polyethylene (PE)), derive from plant Merlon (PC) resin any one or these blend compositions of more than two kinds above-mentioned in add the ionomer deriving from plant.
(2) resin molding of the 2nd embodiment of the present invention be compound more than 1 layer the resin bed (A, B or C layer) deriving from plant as claimed in claim 1 and as the following D layer on top layer or E layer:
D layer: the crystalloid mylar of any one or these blend compositions of more than two kinds above-mentioned comprising polybutylene terephthalate (polybutylene terephthalate, PBT) resin, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin;
E layer: the substantive noncrystalline polyester of any one or these blend compositions of more than two kinds above-mentioned comprising combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, Merlon (PC) resin.
(3) resin molding of the 3rd embodiment of the present invention is compound as the resin bed (A, B or C layer) deriving from plant of above-mentioned 1st embodiment of more than 1 layer in intermediate layer and as the D layer of most top layer and undermost above-mentioned 2nd embodiment or E layer.
(4) resin molding of the 4th embodiment of the present invention is the alternately resin bed (A, B or C layer) deriving from plant of above-mentioned 1st embodiment of compound and the D layer of above-mentioned 2nd embodiment or E layer, and above-mentioned D layer or E layer are most top layer and orlop.
(5) resin molding of the 5th embodiment of the present invention be via or the not resin molding as arbitrary embodiment in the above-mentioned 1st to the 4th of compound more than 2 layers via solid.
(6) resin molding of the 6th embodiment of the present invention is in the above-mentioned resin bed (A deriving from plant, B or C layer) in be blended with the composition forming D layer and (comprise polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, any one of combined polymerization polytrimethylene terephthalate resin, or the crystalloid polyester of these blend compositions of more than two kinds above-mentioned), or the composition forming E layer (comprises combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, any one of Merlon (PC) resin, or the substantive noncrystalline polyester of these blend compositions of more than two kinds above-mentioned).
(7) resin molding of the present invention arranges printed layers between any layer of such as arbitrary resin molding of above-mentioned (1) to (6).
(8) single-layer resin film of the present invention comprises: the blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent.
(9) single-layer resin film of the present invention comprises: the blend composition of polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin deriving from plant, combined polymerization PET (PET) resin and colouring agent; Or derive from the blend composition of polytrimethylene terephthalate (PTT) resin of plant, combined polymerization PET (PET) resin and colouring agent.
(10) double-layer resin film of the present invention to comprise the layer of the blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent deriving from plant as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer or the 2nd layer resin molding.
(11) double-layer resin film of the present invention to comprise the layer of the blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent deriving from plant as the 1st layer;
Thereon, as the 2nd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate (PBT) resin, combined polymerization PET (PET) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin deriving from plant, combined polymerization PET (PET) resin and colouring agent;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer or the 2nd layer resin molding.
(12) double-layer resin film of the present invention to comprise the layer of combined polymerization PET (PET) resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the blend composition of polytrimethylene terephthalate (PTT) resin and colouring agent that derive from plant or in deriving from the blend composition of polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent and then being blended with the layer of resin combination of antistatic agent.
(13) double-layer resin film of the present invention to comprise the layer of combined polymerization PET (PET) resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer of blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent.
(14) three-layer resin film of the present invention is as the 1st layer and the 2nd layer using the formation of the double-layer resin film of above-mentioned (10);
On the 2nd layer, as the 3rd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate (PBT) resin, combined polymerization PET (PET) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin deriving from plant, combined polymerization PET (PET) resin and colouring agent;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer ~ the 3rd layer of resin molding.
(15) three-layer resin film of the present invention to comprise the layer of combined polymerization PET (PET) resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent;
Thereon, as the 3rd layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin, colouring agent and the blend composition of antistatic agent or the blend composition of polybutylene terephthalate (PBT) resin, colouring agent and antistatic agent;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer ~ the 3rd layer of resin molding.
(16) three-layer resin film of the present invention to comprise the layer of combined polymerization PET (PET) resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer of blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent;
Thereon, as the 3rd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent.
(17) three-layer resin film of the present invention to comprise the blend composition layer of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and the colouring agent that derive from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer, superpacket extends the layer of PET (biaxialorientation-polyethylene terephthalate) resin containing twin shaft.
(18) four layers of resin molding of the present invention are as the 1st layer and the 2nd layer using the formation of the double-layer resin film of above-mentioned (10);
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer, compound twin shaft extends PET (BO-PET) resin.
(19) four layers of resin molding of the present invention to comprise the layer of the blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent deriving from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or polybutylene terephthalate (PBT) resin;
And then thereon, as the 4th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(20) four layers of resin molding of the present invention are containing deriving from the layer of blend composition of the blend composition of polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent, polybutylene terephthalate (PBT) resin and colouring agent as the 1st layer using superpacket;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer, composite copolymerization closes PET (PET) resin bed;
And then thereon, as the 4th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(21) five layers of resin molding of the present invention to comprise the layer of the blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and colouring agent or the blend composition of polybutylene terephthalate (PBT) resin and colouring agent deriving from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or polybutylene terephthalate (PBT) resin;
Thereon, as the 4th layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or polybutylene terephthalate (PBT) resin;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(22) five layers of resin molding of the present invention are as the 1st layer and the 2nd layer using the formation of the double-layer resin film of above-mentioned (10);
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer superpacket containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or polybutylene terephthalate (PBT) resin;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(23) five layers of resin molding of the present invention are as the 1st layer and the 2nd layer using the formation of the double-layer resin film of above-mentioned (10);
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer, composite copolymerization closes PET (PET) resin bed;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(24) six layers of resin molding of the present invention are as the 1st layer and the 2nd layer using the formation of the double-layer resin film of above-mentioned (10);
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer complex source in polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or the layer of polybutylene terephthalate (PBT) resin;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin or polybutylene terephthalate (PBT) resin;
And then thereon, as the 6th layer, superpacket is containing the layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber;
Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
(25) resin molding of the present invention is in the resin molding such as any one of above-mentioned (9), (11) to (16), (23), makes 2 ~ 15 % by mole of the terephthalic acid (TPA) of the sour composition as formed combined polymerization PET (PET) resin to form through M-phthalic acid replacement.
(26) resin molding of the present invention is in the resin molding of any one of such as above-mentioned (17), (18), replace with formed twin shaft and extend PET (BO-PET) resin, and 2 ~ 15 % by mole of twin shafts replaced through M-phthalic acid being set to the terephthalic acid (TPA) of the sour composition made as PET extend combined polymerization polyethylene terephthalate resin.
(27) resin molding of the present invention is in the resin molding such as any one of above-mentioned (1) to (26), comprises lubricant in the arbitrary resin bed more than formed one deck.
(28) resin molding of the present invention is formed with embossing jog on the layer on the most top layer becoming the resin molding any one of above-mentioned (1) to (27).
(29) resin molding of the present invention is formed with minute surface on the layer on the most top layer becoming the resin molding any one of above-mentioned (1) to (27).
(30) resin molding of the present invention is in the resin molding such as any one of above-mentioned (2) to (29), and the PTT containing ratio being blended with the resin of PBT and PTT is set to 20 ~ 80%.
(31) of the present invention with resin molding composite decorating board be via or not via solid at least one side and the resin molding compound such as any one of above-mentioned (1) to (30) of substrate.
The effect of invention
According to the present invention, a kind of use can be provided to derive from the resin molding of the raw material of plant, it reduces the amount of petroleum line resin and uses the raw material deriving from plant, to meet the biotic ratio of the mode boosted tree adipose membrane of the condition of biomarker, and give and the previous performance utilizing the resin molding same degree of petroleum plastic cement.
And then, with the adhesion of the decorative panel of this resin molding compound, processability, excellent in te pins of durability on substrate.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the formation of the resin molding representing the 1st embodiment.
Fig. 2 is the skeleton diagram of the formation of the resin molding representing the 2nd embodiment.
Fig. 3 is the skeleton diagram of the formation of the resin molding representing the 3rd embodiment.
Fig. 4 is the skeleton diagram of the formation of the resin molding representing the 4th embodiment.
Fig. 5 is the skeleton diagram of the formation of the resin molding representing the 5th embodiment.
Fig. 6 is the chart of the change of spring rate when being shown in PBT resin the situation being blended with PTT resin.
Detailed description of the invention
Below, the resin molding of the 1st embodiment of the present invention is described.
Fig. 1 represents the skeleton diagram of the formation of the resin molding of the 1st embodiment.The illustration that Fig. 1 (a) is resin molding when being the situation of individual layer, formation when () expression resin molding is the situation of 2 layers b, c () represents the formation of resin molding when being the situation of 3 layers, formation when (d) represents that resin molding is the situation of 4 layers.
Resin molding comprises A layer, B layer or C layer.
When resin molding is the situation of A layer, comprise polytrimethylene terephthalate (PTT) resin deriving from plant, PET (PET) resin deriving from plant, the olefin-based resin (polypropylene (PP), polyethylene (PE)) deriving from plant, any one or these blend compositions of more than two kinds above-mentioned of Merlon (PC) resin of deriving from plant.
When resin molding is the situation of B layer, be included in polytrimethylene terephthalate (PTT) resin deriving from plant, derive from PET (PET) resin of plant, derive from the olefin-based resin (polypropylene (PP) of plant, polyethylene (PE)), derive from any one of Merlon (PC) resin of plant, or add the compatilizer deriving from plant in these blend compositions of more than two kinds above-mentioned and the elastomer deriving from plant (derives from the compatilizer of plant, the elastomer deriving from plant can be any one).
When resin molding is the situation of C layer, be included in polytrimethylene terephthalate (PTT) resin deriving from plant, PET (PET) resin deriving from plant, the olefin-based resin (polypropylene (PP), polyethylene (PE)) deriving from plant, derive from plant Merlon (PC) resin any one or these blend compositions of more than two kinds above-mentioned in add the ionomer deriving from plant.
Herein, what is called derives from the composition of plant, refers to the composition using the material generated by plant as its initiation material.Such as, as the polytrimethylene terephthalate resin (PTT) deriving from plant forming A layer, B layer, C layer, can enumerate and be produced by terephthalic acid (TPA) and 1,3 propane diols that derive from plant.
In addition, as the polyethylene terephthalate resin (PET) deriving from plant forming A layer, B layer, C layer, can enumerate: in the terephthalic acid (TPA) (mass ratio 70%) and monoethylene glycol (mass ratio 30%) of the raw material as PET, monoethylene glycol be replaced with the biological raw material from sugarcane and manufacture etc.
As the olefin-based resin (polypropylene (PP), polyethylene (PE)) deriving from plant forming A layer, B layer, C layer, make the ethylene glycol deriving from plant become raw material, can enumerate low density polyethylene (LDPE), wire low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, ethylene/vinyl acetate, ethylene/ethyl acrylate copolymer, ethylene/methyl acrylate copolymer and above-mentioned these copolymer, through fusion or cross-linking agent etc.
As Merlon (PC) resin deriving from plant forming A layer, B layer, C layer, the Merlon etc. comprising alcohol from sugar and polyglycols disclosed in Japanese Patent Laid-Open 2011-241277 publication etc. can be enumerated.
As the copolymer resin forming E layer, as sour composition, that a part for terephthalic acid (TPA) is replaced through the structure of other dicarboxylic acids, as other dicarboxylic acid component during this situation, oxalic acid, malonic acid, butanedioic acid, adipic acid, azelaic acid, decanedioic acid, neopentanoic acid, M-phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, P-hydroxybenzoic acid etc. can be enumerated.Moreover other dicarboxylic acid component can be a kind of resin be selected from above-mentioned cited dicarboxylic acid component, or also can be the mixture of the combination comprising more than two kinds.In addition, the amount of other dicarboxylic acids replaced can suitably be selected.
In addition, as alcohol composition, such as, also can be and a part for ethylene glycol is replaced through other diol components.
As other diol components during this situation, propane diols, 1 can be enumerated, ammediol, BDO, hexylene glycol, diethylene glycol, neopentyl glycol, poly-stretch alkyl diol, 1,4-CHDM, glycerine, new penta tetrol, three methyl alcohol, methoxyl group is poly-stretches alkyl diol etc.Moreover other diol components can be a kind of resin be selected from above-mentioned cited diol component, or also can be the mixture of the combination comprising more than two kinds.In addition, the amount of other glycol replaced can suitably be selected.
And then the resin forming A, B, C, D layer also can comprise above-mentioned combined polymerization composition.
In the compound resin masking that cladding as above is formed, if the melting viscosity under the shear rate measured by selection gist JIS-K7199 10 [1/s] becomes 1000 [Pas] and resin temperature difference becomes within 30 DEG C, is preferably within 15 DEG C and then is preferably the combination of the resin within 5 DEG C, then can commercially available any one resin of choice for use.
< compatilizer >
In B layer, in order to fusion composition is mixed equably, can mixed source in the compatilizer of plant.Combined amount is suitably selected according to purposes.
As compatilizer, be preferably use and derive from the resins such as the vinyl copolymer of plant.
As the example of the compatilizer of this kind of vinyl copolymer, include, for example: the vinyl-vinyl acetate copolymer deriving from plant, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene methyl methacrylate copolymer, ethane-acetic acid ethyenyl ester-maleic anhydride terpolymer, ethylene-ethylacrylate-maleic anhydride terpolymer, ethylene-methyl methacrylate glycidyl ester copolymer, ethane-acetic acid ethyenyl ester-GMA terpolymer, ethylene-ethylacrylate-GMA terpolymer.
Wherein, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer can preferably be used.
In addition, also can also with compatilizers more than 2 kinds.
As the elastomer deriving from plant of B layer, can use to derive from the thermoplastic polyester elastomer etc. of 1,3-PD as raw material of plant.Specifically, the commodity that include, for example E.I.Du Pont Company's manufacture are called Hytrel RS etc.
In addition, the environment amity composition for thermoplastic elastomer etc. comprising more than the resin 25 quality % deriving from plant disclosed in Japanese Patent Laid-Open 2010-254729 publication etc. can also be used.
As the ionomer deriving from plant of C layer, include, for example: the ethylene-methacrylic acid copolymer ionomer deriving from plant, ethylene-acrylic acid copolymer ionomer, propylene-methacrylic acid copolymer ionomer, propylene acrylic acid terpolymer ionomer polymer, butene-propylene acid copolymer ionomer, vinyl-vinyl sulfonic acid copolymer ionomer, Styrene-methyl Acrylic Acid Copolymer ionomer, sulfonated polystyrene ionomer, fluorine system ionomer, distant pawl PBAA ionomer, sulfonate ethylene-propylene-diene copolymers ionomer, water elementization polypenthylene ionomer, polypenthylene ionomer, poly-(vinylpyridine salt) ionomer, poly-(vinyl trimethyl ammonium salt) ionomer, poly-(vinyl benzyl microcosmic salt) ionomer, styrene-butadiene acrylic copolymer ionomer, polyurethane ionomer, sulfonated phenylethylene-2-acrylamide-2-methylpropane chlorosulfuric acid ionomer, acid-amine ionomer, fat family ionomer, fragrance family ionomer etc.
By fusion compatilizer, derive from the elastomer of plant or derive from the ionomer of plant, can be made into the raw material containing ratio and the resin molding improving processability or adhesion that do not reduce and derive from plant.
Moreover, in Fig. 1 (b) to (d), exist compound phase with resin bed (A, B or C layer) and form the situation of resin molding, even if but be identical resin bed, the situation that the composition components contained by also existing in layer is different.Such as, also there is the situation of the layer that compound makes compatilizer, elastomer, ionomer different respectively.
The situation of embodiment illustrated below also can be same.
The resin molding of the 2nd embodiment of the present invention is shown in Fig. 2.
The illustration that Fig. 2 (a) is resin molding when being the situation of 2 layers, formation when (b) represents that resin molding is the situation of 3 layers, formation when (c) represents that resin molding is the situation of 4 layers.
The resin molding of above-mentioned 1st embodiment of the resin molding compound more than 1 layer of the 2nd embodiment and as the following D layer on top layer or E layer.
D layer: comprise the crystalloid mylar of any one or these blend compositions of more than two kinds above-mentioned comprising polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin.
E layer: comprise the substantive noncrystalline polyester of any one or these blend compositions of more than two kinds above-mentioned comprising combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, Merlon (PC) resin.
Moreover D layer, E layer are for comprising the layer of the previous resinous principle from oil.
In the resin molding of the 2nd embodiment, by the cladding resin molding forming the resin molding combining the composition making adhesion promote, the splitting of resin molding can be suppressed.
Namely, by compound D layer on the resin molding deriving from plant, E layer, namely, polybutylene terephthalate (PBT) resin is comprised as previous resin, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, any one of combined polymerization polytrimethylene terephthalate resin, or the crystalloid polyester of these blend compositions of more than two kinds above-mentioned, or comprise combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, any one of Merlon (PC) resin, or the layer of the substantive noncrystalline polyester of these blend compositions of more than two kinds above-mentioned, can be made into the cladding resin molding of the surface characteristic remaining equal with previous product.
The resin molding of the 3rd embodiment of the present invention is shown in Fig. 3.
The illustration that Fig. 3 (a) is resin molding when being the situation of 3 layers, formation when () expression resin molding is the situation of 4 layers b, c () represents the formation of resin molding when being the situation of 5 layers, formation when (d) represents that resin molding is the situation of 6 layers.
The resin molding of the 3rd embodiment comprises using the resin molding of above-mentioned 1st embodiment of more than 1 layer as intermediate layer and in most top layer and the above-mentioned D layer of orlop compound or E layer.
Namely, polybutylene terephthalate (PBT) resin is comprised as previous resin by the levels compound of resin molding deriving from plant, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, any one of combined polymerization polytrimethylene terephthalate resin, or the crystalloid polyester of these blend compositions of more than two kinds above-mentioned, or comprise combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, any one of Merlon (PC) resin, or the layer of the substantive noncrystalline polyester of these blend compositions of more than two kinds above-mentioned, can be made into and maintain the surface characteristic equal with previous product and the cladding resin molding of adhesion.
The resin molding of the 4th embodiment of the present invention is shown in Fig. 4.
The illustration that Fig. 4 (a) is resin molding when being the situation of 3 layers, formation when (b) represents that resin molding is the situation of 5 layers, formation when (c) represents that resin molding is the situation of 7 layers.
The resin molding of the 4th embodiment is the resin molding of alternately above-mentioned 1st embodiment of compound and above-mentioned D layer or E layer, and D layer or E layer are most top layer and orlop.
Namely, by forming resin (D layer or E layer) that alternately compound is previous and deriving from the formation of resin (A layer, B layer or C layer) of plant, can be made into the raw material containing ratio that do not reduce and derive from plant and maintain the surface characteristic equal with previous product and the cladding resin molding of adhesion.
The resin molding of the 5th embodiment of the present invention is shown in Fig. 5.
The illustration that Fig. 5 (a) is resin molding when being the situation of 4 layers, formation when (b) represents that resin molding is the situation of 6 layers, formation when (c) represents that resin molding is the situation of 10 layers.
Moreover Fig. 5 (a) is the resin molding of compound 2 layers of Fig. 2 (a), Fig. 5 (b) is the resin molding of compound 2 layers of Fig. 3 (a), and Fig. 5 (c) is the resin molding of compound 2 layers of Fig. 4 (b).
The resin molding of the 5th embodiment be via or not via solid compound more than 2 layers if above-mentioned 1st embodiment is to arbitrary resin molding of the resin molding of the 4th embodiment, therefore can be made into the raw material containing ratio that do not reduce and derive from plant and maintain the surface characteristic equal with previous product and the cladding resin molding of adhesion.
The resin molding of other the 6th embodiments of the present invention is in above-mentioned A, composition (the D layer: comprise polybutylene terephthalate (PBT) resin forming D layer is blended with in B or C layer, polytrimethylene terephthalate (PTT) resin, PET (PET) resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, any one of combined polymerization polytrimethylene terephthalate resin, or the crystalloid mylar of these blend compositions of more than two kinds above-mentioned), or the composition forming E layer (comprises combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, any one of Merlon (PC) resin, or the substantive noncrystalline polyester of these blend compositions of more than two kinds above-mentioned).
Namely, by being formed with the resin molding of the previous resin of the degree fusion not reducing the raw material containing ratio deriving from plant, can be made into the resin molding deriving from plant of the composition promoting adhesion, can be made into the splitting suppressing resin molding or the resin molding promoting adhesion.
Especially, cladding form resin molding and on base material the film composite wood of this resin molding of compound can concentrate in adding the stress alleviated man-hour to so-called weak boundary layer (Weak Boundary Layer, WBL), can promote tunicle peel off inhibition.Therefore, can preferably for high degree of finish purposes.
Moreover, in above-mentioned resin molding, in time requiring the situation of anti-flammability or durability to each resin molding, in order to give anti-flammability, resistance to hydrolyzable or weatherability, can the various additive of fusion.
In addition, such as also can suitably allocate: organic or inorganic filler, resist and be adhered agent, crystallization promoter, nucleator, adsorbent, age resister (ester, acid amides etc.), antioxidant, antiozonant, ultra-violet absorber, infrared absorbent, photostabilizer, light stabilizer, stick together imparting agent, plasticiser (stearic acid, the aliphatic acid such as oleic acid or these slaine etc.), softening agent (mineral oil, wax, paraffin class etc.), stabilizing agent, heat stabilizer, lubricant, releasing agent, antistatic agent, end sealant, polymerization inhibitor, crosslinking agent, denaturant, colouring agent (comprises coloring pigment, the film coloured materials such as illuminating colour), coupling agent, anticorrisive agent, mould inhibitor, fire retardant, flame retardant, anti-covered with clouds dose, the elevator of resistance to abrasion, delustering agent, deodorant, ion-exchanger, the additives such as refractive index adjusters.
And then also optionally can implement embossing processing in the surface of above-mentioned resin molding and form embossing jog, giving has relief high design, or implements minute surface arrangement processing.
In addition, also gloss adjustment layer can be set in the surface of above-mentioned resin molding.As gloss adjustment layer, can be water white transparency, or also can be tinted clear, and then also can be the transparent of delustring, be glossiness in order to adjust surface resin film and arrange, also can be the effect of the layer (hard conating) giving protection surface.
The above > of < biology degree 25wt%
Moreover in the resin molding of this embodiment, the biological degree of resin molding entirety is more satisfactory is more than 25wt%.
Its reason is, the biological degree by resin molding entirety is more than 25wt%, can obtain the biological plastic cement identification mark that Japanese biological plastic cement association (JBPA) assert, can give surcharge as the less proprietary concentrate of carrying capacity of environment to resin molding.
< biomarker >
Herein, biomarker used in the present invention is described.
The identification of biomarker has been carried out to using the commodity of biomaterial social legal person organic resource association of Japan (JORA).Assert that the object of biomarker is, biomarker is given by the commodity utilizing and apply flexibly biomaterial to produce, consumer can be made to know the utilization of bio-commodities and apply flexibly, promote the utilization of biomaterial by these commodity universal, utilize naturally present to contribute to the construction of the society of sustainable development.
In addition, about use as PLA by biological raw material the situation of biomaterial of being produced, the biological plastic cement association (JBPA) of Japan is in view of the viewpoint preventing greenhouse effects of the earth, and reduction fossil resource consume importance and to having formulated the identification certification mark system of biological plastic cement containing the material from organic resource (plant etc.) more than specified quantitative as the biological plastic cement products of plastic cement constituent, the product being suitable for the benchmark that this association is assert is regarded as " biological plastic cement ", allow to enable ordinary consumer easily identify biological plastic cement products to use sign flag.
In order to carry out biological plastic cement identification identification, the plastic cement products must be biological plastic cement degree in product (composition from biology in biological plastic cement composition contained in raw material, product is relative to the ratio of total amount) being more than 25wt%.Namely, consider the load to earth environment, it is highly important that the biomaterial ratio (minimum is more than 25wt%) improved as far as possible in resin molding, if consider, consumer is understood as surcharge, be then necessary to obtain biological plastic cement identification mark.
The present inventor etc. think in view of above-mentioned purport, and resin molding of the present invention is also more satisfactory is improve biomaterial ratio as far as possible.
< printed layers >
Resin molding of the present invention can arrange printed layers between any layer of resin molding of the present invention.
That is, in resin molding, in order to painted or formation decorative pattern, also printed layers can be formed.In addition, be replaced into the printing-ink containing the ester compounds obtained by the alcohol from biology or the compound with hydroxyl from biology by part or all of the petroleum solvent using the solvent as ink, also can utilize and not damage printing adaptability and the ink to environment gentleness of the balancing good of the evaporation drying of ink and machine stability forms printed layers.
Decorative panel of the present invention be via or not via solid in substrate at least one side and resin molding compound of the present invention.
Be excellent with the adhesion of the substrate such as metallic plate with arbitrary resin molding composite decorating board of the present invention on substrate, also there is not the splitting of resin molding or the stripping with substrate during processing decoration plate, various formed products can be processed into.
< solid >
As the solid that the compound of resin molding compound each other or resin molding and substrate uses, due to fire prevention, without foul smell, price cheapness, so the emulsion-type solid of common solid, such as Polyester, acrylic acid series, vinyl acetate resin system, vinyl acetate resins system, carbamide resin system, urethane resin system etc. preferably can be used.
In addition, the heat curing-type solid, polyester urethane resin system solid etc. of the emulsion-type solid or epoxy-phenol resins system etc. of polyester urethane resin system etc. can also be used.
Moreover solid is not limited to illustrated in these.
In addition, as the resin of composition that can be used as solid, the resin for A, B, C layer can be preferably used to have the resin of reactivity or compatibility.What is called has reactivity or compatibility, refer to have the functional group higher with the compatibility of the resin of A, B, C layer or can with the functional group of the resin of reaction A, B, C layer.As the example of functional group with this kind of characteristic, the functional groups such as anhydride group, carboxylic acid group, carboxylic acid ester groups, carboxyl acyl chloride base, carboxylic acyloxy amido, carboxyl acyl chloride base, sulfonic group, sulfonate group, sulfuryl chlorio, sulfonic acid amides base, sulfuryl chlorio, epoxy radicals, amido, imide or oxazoline group can be enumerated.
Moreover, in time making the situation of resin molding compound each other, being positioned at the compound between resin molding about printed layers, by using the mediator etc. printing-ink to adherence, even if do not arrange adhesion agent layer especially, also can carrying out compound.
< lubricant >
As lubricant, can use: the ester of aliphatic hydrocarbon system, senior aliphat alcohol, aliphatic acid, fatty acid metal salts, aliphatic acid or the organic system lubricant such as amide derivatives, such as stearic acid amide, oleamide, erucyl amide, erucamide, behenic acid acid amides, ethylene bis-oleamide; Or the lubricant that inorganic base lubricants such as silicon system, zeolite, calcium carbonate, silica, aluminium oxide, barium sulfate such as silicon, alumina silicate, magnesium silicate etc. are usually commercially available.
In addition, in utilize extruder mix in resin lubricant time, with regard to preventing the viewpoint of the blocking of the filter in extruder, true degree lubricant is better than unsetting lubricant, but unsetting lubricant can show the effect made with lubricator significantly.
As above-mentioned lubricant, be use average grain diameter to be 0.5 ~ 10 μm, to be preferably the attritive powder of 1 ~ 5 μm.This attritive powder be in the then resin bed of decorating film containing 0.05 ~ 3 quality %, be preferably containing 0.1 ~ 0.3 quality %.By containing the attritive powder of the particle diameter with above-mentioned proper range with proper range in resin containing ratio, and the shape of batching improving film in not damaging excellent design when also obtains the effect preventing gauffer from producing.
But, be not limited to as mentioned above.
In addition, except lubricant as above, also can add: light stabilizer, free radical scavenger, antioxidant etc., processing procedure stabilizing agent, metal-inert agent etc. generally for and promote the heat resistance of resin, weatherability and adding; Or processing aid, other generally for the processability and the various additives that add that promote resin.
< antistatic agent >
As antistatic agent, nonionic system antistatic agent, cation system antistatic agent, both sexes system antistatic agent etc. can be used, especially can preferably use cation system.When situation for cation system, the anti-static effect especially with regard to being arranged at the coating layer on film surface can play with regard to the aspect to surface when forming decoration sheet, comparatively excellent, can reach this effect to heavens.In cation system antistatic agent, especially be preferably and be used in the polymer that main chain has pyridine ring, as concrete example, diallyl dimethyl ammoniumchloride, poly-(diallyldimethylammonium chloride/alkyl dimethyl ammonium chloride/N hydroxymethyl acrylamide) etc. can be enumerated.
But, be not limited to as mentioned above.
< ultra-violet absorber >
As ultra-violet absorber, preferably can use that triazine (triazine) is, benzophenone series, BTA system, benzoic ether system, cyanoacrylate system, salicylate system etc.
In addition, by containing hindered amine system light stabilizer, heat stabilizer, antioxidant, and then UV degradation preventing effectiveness can be promoted.
But, be not limited to as mentioned above.
In the manufacture of resin molding, mixed melting can be carried out to the resin combination forming each resin molding and mix and use.Mix the melting muller that can use and usually use, and simultaneously makes resin molding, be therefore preferably use two-axis extruder owing to can simultaneously carry out mixing.Or, two-axis extruder also can be used to carry out mixing, being squeezed into rope form, make its granulating and use.The resin molding obtained can by so that extend and filming, high strength in single shaft direction or biaxially oriented.
In addition, also shrinkage factor can be adjusted by the heat fixation temperature after adjustment extension.The usual ways such as extension can adopt extension between roller, tentering method extends, tubular type extends, the twin shaft extension simultaneously of tentering method.
These composite membranes can be produced by generally well-known method.Such as, solid also can be utilized to carry out dry lamination and compound to the 1st layer and the 2nd layer.
In addition, also can adopt one side on the resin molding of the 1st layer, extrude the laminating of the 2nd laminated formation composite resin membrane.
In addition, also can carry out extruding by utilizing the extruder of more than 3 simultaneously and in charging module or nozzle compound co-extrusion pressure method and produce.
Wherein, co-extrusion platen press carries out producing and efficiency is also higher, so the best is owing to can utilize to extrude for 1 time.Co-extrusion platen press can use T-shaped die head method, and circle also can be used to get to know method.
In addition, the film obtained, by carrying out uniaxial extension, twin shaft extension, also can promote hot strength, impact strength.
And then, as the film-forming method making resin molding be complex as cladding, also can use commercially available film and utilize backer roll etc. to carry out compound, the film-forming method that Japanese Patent Laid-Open 11-42744 publication, Japanese Patent Laid-Open 2006-69139 publication, Japanese Patent Laid-Open 2006-159537 publication, Japanese Patent Laid-Open 2008-030258 publication etc. also can be utilized to disclose is filmed.
(effect of PTT resin fusion)
Fig. 6 is the chart of the change of spring rate when being shown in PBT resin the situation being blended with PTT resin.During known arbitrary situation in for monomer, temperature becomes higher, then the spring rate of PBT resin, PTT resin becomes less.
But the Tg (glass transition temperature) of PBT resin, PTT resin is about 45 DEG C, according to Fig. 6, the spring rate of the PBT/PTT blending resin in this temperature province known shows value excellent especially.
That is, when the containing ratio of PTT resin is the situation of 20 ~ 80%, the spring rate display minimum at 45 DEG C.
Therefore, the result according to Fig. 6, if known, PTT resin containing ratio is set to 20 ~ 80%, is preferably 30 ~ 70% and then be preferably 40 ~ 60%, then the processability near Tg becomes good.
Usually, in higher than when forming the situation of processing in the temperature province of Tg, easily cause the attachment of instrument etc. or coarse etc. the problem of resin layer surface, in order to ensure processability, must processing temperature be improved and reduce spring rate, therefore must carry out temperature setting in the mode obtaining its balance.
But, as mentioned above, in PBT/PTT blending resin, make PTT containing ratio optimization, be namely convenient to by this, in the temperature province near Tg, also can reduce spring rate, its result, the resin bed that processability is good can be obtained.
In addition, known, utilize this kind of PBT/PTT blending resin to promote the effect of processability, the not only film of this blending resin individual layer, and by being arranged at least any layer of the resin molding that cladding is formed, also can obtain fully.Although the details of its mechanism is not still clear and definite, inferring that its reason is, obtaining by arranging the lower layer of spring rate the stress dispersion effect adding man-hour, so the processability of tunicle entirety promotes.
Moreover spring rate is based on JIS K 7161 (test method of plastic cement-tensile properties) and obtains as follows.
First, polyester resin film is cut into the tensile test specimen of width 5mm, length 50 ~ 60mm.
Utilize the cupping machine (Tensilon) under making mensuration environment be held in specific design temperature, under the condition of action bars interval 20mm, draw speed 200mm/min, nominal stress-extension curve is measured to this tensile test specimen, obtains nominal stress σ 0 and percentage elongation El.
Percentage elongation El can obtain according to following formula.
El＝100×(L－L0)/L0
Herein, L0 is the length of the test portion before stretching, and L is the length of the test portion after stretching.
In obtained nominal stress-extension curve, according to the slope of the linear scope maintained near percentage elongation 2 ~ 4%, utilize least squares method, and obtain spring rate E according to following formula.
E＝Δσ0/ΔEl×100
Embodiment
Below, the present invention will be described in more detail to utilize embodiment.
< embodiment 1 >
Being formed by the layer of resin molding as being set to as Suo Shi Fig. 2 (a) is 2 layers of formation of D layer (PBT resin)/A layer (deriving from the PTT of plant) from top to bottom, and is set to D layer thickness: the thickness of 50 μm/A layer: 150 μm.
Secondly, with the mode of A layer contact substrate (galvanized steel plain sheet) via solid this double-layer resin film of compound.
Then, use squeezer to carry out bending process, result at processing temperature 45 DEG C, the good products formed of the stripping without resin molding can be obtained, the possibility being used as decorative panel can be confirmed.
< embodiment 2 >
Being formed by the layer of resin molding as being set to as Suo Shi Fig. 3 (a) is 3 layers of formation of E layer (combined polymerization PET resin)/B layer (deriving from the PC of plant)/D layer (admixture of PBT and PET) from top to bottom, manufactures E layer thickness: 50 μm/B layer thickness: 150 μm/D layer thickness: the composite resin membrane of 50 μm.
Then, use squeezer to carry out bending process, result at processing temperature 45 DEG C, the good products formed of the stripping without resin molding can be obtained, the possibility being used as decorative panel can be confirmed.
< embodiment 3 >
The resin molding of embodiment 3 is set to monofilm, is formed as comprising the resin molding of the blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and the colouring agent that derive from plant.
As the polytrimethylene terephthalate resin (PTT) deriving from plant, can enumerate and be produced by terephthalic acid (TPA) and 1,3 propane diols that derive from plant.
As polybutylene terephthalate (PBT) resin, previous resin can be used under the degree not reducing the raw material containing ratio deriving from plant.
By this, adhesion can be promoted.Can be made into the resin molding promoting adhesion.
Moreover, as colouring agent, can enumerate and comprise the film such as coloring pigment, illuminating colour coloured material.
The resin molding of embodiment 3 is that the blend composition through polytrimethylene terephthalate (PTT) resin deriving from plant of extruder heating and melting, polybutylene terephthalate (PBT) resin, colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) is squeezed in from T-shaped die head monofilm casting roller being made thickness 100 μm.
As lubricant, masterbatch (comprising the unsetting lubricant 5 quality % of average grain diameter 5 μm) the 3 quality % that DIC limited company manufactures are mixed, adjust in the mode containing lubricant 0.15 quality % in this resin.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=51 quality %).
< embodiment 4 >
The resin molding of embodiment 4 is set to monofilm, make comprise polybutylene terephthalate (PBT) resin, the resin molding of the blend composition that derives from polytrimethylene terephthalate (PTT) resin of plant, combined polymerization PET (PET) resin and colouring agent.
Or, make the resin molding of the blend composition comprising polytrimethylene terephthalate (PTT) resin, combined polymerization PET (PET) resin and the colouring agent that derive from plant.
The resin molding of embodiment 4 be using through extruder heating and melting polytrimethylene terephthalate (PTT) resin deriving from plant, polybutylene terephthalate (PBT) resin, be squeezed in from T-shaped die head monofilm casting roller being made thickness 90 μm as PET (PET) resin of the M-phthalic acid 15mol% combined polymerization of sour composition and the blend composition of colouring agent (pigment 4 quality %).
Moreover the fusion mass ratio of PTT, PBT and PET is set to 3:1:1 (PTT containing ratio=57.6 quality %).
< embodiment 5 >
The resin molding of embodiment 5 is set to duplicature, be formed as following resin molding, it derives from polytrimethylene terephthalate (PTT) resin of plant by comprising, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent is as the 1st layer, thereon, as the 2nd layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent.
Further, the blending resin of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin deriving from plant is comprised in the layer more than at least one deck of the 1st layer or the 2nd layer resin molding.
The resin molding of embodiment 5 utilizes co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent (pigment 15 quality %), with polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) is squeezed in from T-shaped die head duplicature casting roller being made thickness 100 μm with Thickness Ratio 4:1.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT and PBT is 2 kinds that are set to 3:2 (PTT containing ratio=51 quality %) and 9:1 (PTT containing ratio=76.5 quality %).
< embodiment 6 >
The resin molding of embodiment 6 is set to duplicature, be formed as following resin molding: it derives from polytrimethylene terephthalate (PTT) resin of plant by comprising, the blend composition layer of polybutylene terephthalate (PBT) resin and colouring agent is as the 1st layer, thereon, as the 2nd layer, superpacket is containing polybutylene terephthalate (PBT) resin, the blend composition of combined polymerization PET (PET) resin and colouring agent, or polybutylene terephthalate (PBT) resin, derive from polytrimethylene terephthalate (PTT) resin of plant, the layer of the blend composition of combined polymerization PET (PET) resin and colouring agent.
Further, the blending resin of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin deriving from plant is comprised in layer more than at least one deck of 1st layer or the 2nd layer resin molding.
The resin molding of embodiment 6 utilizes co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, polybutylene terephthalate (PBT) resin, make the blend composition of PET (PET) resin as the M-phthalic acid 15mol% combined polymerization of sour composition and colouring agent (pigment 40 quality %), with polytrimethylene terephthalate (PTT) resin deriving from plant, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 40 quality %) and lubricant (0.15 quality %) is squeezed in from T-shaped die head duplicature casting roller being made thickness 90 μm with Thickness Ratio 1:2.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT, PBT and PET is set to 2:1:2 (PTT containing ratio=24 quality %), the fusion mass ratio of PTT and PBT is set to 1:1 (PTT containing ratio=30 quality %).
< embodiment 7 >
The resin molding of embodiment 7 is set to duplicature, be formed as following resin molding: its layer that will comprise combined polymerization PET (PET) resin is as the 1st layer, thereon, as the 2nd layer superpacket containing the blend composition of polytrimethylene terephthalate (PTT) resin and colouring agent that derive from plant or in deriving from the blend composition of polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent and then being blended with the layer of resin combination of antistatic agent.
As antistatic agent, Sanyo is used to change into the Pelestat NC632110 quality % of Industries, Inc's manufacture.
The resin molding of embodiment 7 utilizes co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, polybutylene terephthalate (PBT) resin and antistatic agent (10 quality %), the blend composition of colouring agent (pigment 30 quality %), with the blend composition of PET (PET) resin made as the M-phthalic acid 15mol% combined polymerization of sour composition and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 40 μm with Thickness Ratio 4:1.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=36 quality %).
< embodiment 8 >
The resin molding of embodiment 8 is set to duplicature, the layer of combined polymerization PET (PET) resin will be comprised as the 1st layer, thereon, as the 2nd layer superpacket containing the layer of blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent.
The resin molding of embodiment 8 be utilize co-extrusion pressure using through polytrimethylene terephthalate (PTT) resin deriving from plant of extruder heating and melting, polybutylene terephthalate (PBT) resin and colouring agent (pigment 20 quality %) blend composition, with PET (PET) resin making the M-phthalic acid 15mol% combined polymerization as sour composition, be squeezed in from T-shaped die head duplicature casting roller being made thickness 70 μm with Thickness Ratio 4:1.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=48 quality %).
< embodiment 9 >
The resin molding of embodiment 9 is set to trilamellar membrane, be formed as following resin molding: using the formation of the double-layer resin film described in embodiment 10 as the 1st layer and the 2nd layer, on the 2nd layer, as the 3rd layer, superpacket is containing polybutylene terephthalate (PBT) resin, the blend composition of combined polymerization PET (PET) resin and colouring agent, or polybutylene terephthalate (PBT) resin, derive from polytrimethylene terephthalate (PTT) resin of plant, the layer of the blend composition of combined polymerization PET (PET) resin and colouring agent.
Further, comprise in layer more than at least one deck of 1st layer ~ the 3rd layer of resin molding derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 9 utilizes co-extrusion pressure by polybutylene terephthalate (PBT) resin through extruder heating and melting, make the blend composition of PET (PET) resin as the M-phthalic acid 15mol% combined polymerization of sour composition and colouring agent (pigment 4 quality %), derive from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent (pigment 4 quality %), with polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 4 quality %) and lubricant (0.15 quality %), be squeezed in from T-shaped die head trilamellar membrane casting roller being made thickness 90 μm with Thickness Ratio 2:3:1.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PBT and PET is set to 1:1, the fusion mass ratio of PTT and PBT is 2 kinds that are set to 3:2 (PTT containing ratio=57.6 quality %) and 4:1 (PTT containing ratio=76.8 quality %).
< embodiment 10 >
The resin molding of embodiment 10 is set to trilamellar membrane, be formed as following resin molding: its layer that will comprise combined polymerization PET (PET) resin is as the 1st layer, thereon, as the 2nd layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent, thereon, as the 3rd layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent and antistatic agent, or polybutylene terephthalate (PBT) resin, the layer of the blend composition of colouring agent and antistatic agent.
Further, the blending resin of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin deriving from plant is comprised in layer more than at least one deck of 1st layer ~ the 3rd layer of resin molding.
The resin molding of embodiment 10 makes as follows.
Utilize co-extrusion pressure by polybutylene terephthalate (PBT) resin through extruder heating and melting, antistatic agent (10 quality %), and the blend composition of colouring agent (pigment 30 quality %), derive from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent (pigment 30 quality %), with the blend composition of PET (PET) resin made as the M-phthalic acid 15mol% combined polymerization of sour composition and lubricant (0.15 quality %), be squeezed in from T-shaped die head trilamellar membrane casting roller being made thickness 40 μm with Thickness Ratio 1:2:1.
Lubricant is that use is identical with embodiment 3.Antistatic agent is that use is identical with embodiment 7.
Moreover the fusion mass ratio of PTT and PBT is set to 1:1 (PTT containing ratio=35 quality %).
< embodiment 11 >
The resin molding of embodiment 11 is set to trilamellar membrane, be formed as following resin molding: its layer that will comprise combined polymerization PET (PET) resin is as the 1st layer, thereon, as the 2nd layer, superpacket is containing the blending resin of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin that derive from plant, or polybutylene terephthalate (PBT) resin, and the layer of the blend composition of colouring agent, thereon, as the 3rd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent.
The resin molding of embodiment 11 utilizes co-extrusion pressure by polybutylene terephthalate (PBT) resin through extruder heating and melting, and the blend composition of colouring agent (pigment 20 quality %), derive from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent (pigment 20 quality %), with PET (PET) resin of the M-phthalic acid 15mol% combined polymerization made as sour composition, be squeezed in from T-shaped die head trilamellar membrane casting roller being made thickness 70 μm with Thickness Ratio 2:2:1.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=48 quality %).
< embodiment 12 >
The resin molding of embodiment 12 is set to trilamellar membrane, be formed as following resin molding: its blend composition layer deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and colouring agent using comprising is as the 1st layer, thereon, printed layers is formed as the 2nd layer, thereon, as the 3rd layer, superpacket extends the layer of PET (BO-PET) resin containing twin shaft.
The resin molding of embodiment 12 is that the blend composition through polytrimethylene terephthalate (PTT) resin deriving from plant of extruder heating and melting, polybutylene terephthalate (PBT) resin, colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) is squeezed in from T-shaped die head film casting roller being made thickness 50 μm.In the lower surface of commercially available twin shaft extension PET (BO-PET) film of thickness 25 μm, utilize gravure rotary machine printed solid printed layers and pattern printed layers, printed layers is overlapped, the feed speed in the heating-up temperature 120 DEG C of crimping roller, resin molding: 20m/min, crimping pressure rolling pressure with above-mentioned colored resin layer: add thermo-compressed to two films under the condition of 2.45MPa and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=51 quality %).
< embodiment 13 >
The resin molding of embodiment 13 is set to four tunics, be formed as following resin molding: using the formation of the double-layer resin film described in embodiment 10 as the 1st layer and the 2nd layer, on the 2nd layer, printed layers is formed as the 3rd layer, thereon, as the 4th layer, compound twin shaft extends PET (BO-PET) resin.
The resin molding of embodiment 13 utilizes co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent (pigment 15 quality %), with polytrimethylene terephthalate (PTT) resin deriving from plant, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %) and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 60 μm with Thickness Ratio 4:1.
Thereafter, in the lower surface of commercially available twin shaft extension PET (BO-PET) film of thickness 25 μm, utilize gravure rotary machine printed solid printed layers and pattern printed layers, make the colored resin layer side superimposed that printed layers and above-mentioned lubricant do not enter, the feed speed in the heating-up temperature 120 DEG C of crimping roller, resin molding: 20m/min, crimping pressure rolling pressure: under the condition of 2.45MPa, thermo-compressed is added to two films and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT and PBT is 2 kinds that are set to 3:2 (PTT containing ratio=51 quality %) and 1:3 (PTT containing ratio=21.3 quality %).
< embodiment 14 >
The resin molding of embodiment 14 is set to four tunics, be formed as following resin molding: it derives from polytrimethylene terephthalate (PTT) resin of plant by comprising, the blend composition layer of polybutylene terephthalate (PBT) resin and colouring agent is as the 1st layer, thereon, printed layers is formed as the 2nd layer, thereon, as the 3rd layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin, or the layer of polybutylene terephthalate (PBT) resin, and then thereon, as the 4th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, the blending resin of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin deriving from plant is comprised in layer more than at least one deck of the resin molding beyond printed layers.
Herein, as ultra-violet absorber, BTA system ultraviolet radiation absorption masterbatch (comprising the Adekastab LA-3120 quality % that Adeka Corp. manufactures) the 10 quality % that DIC limited company manufactures are mixed, adjusted in the mode comprising ultra-violet absorber 2.0 quality % in this resin.
The resin molding of embodiment 14 be utilize co-extrusion pressure by through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), lubricant (0.15 quality %) blend composition, with the blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 45 μm with Thickness Ratio 1:8.In the layer surface not comprising ultra-violet absorber of this duplicature, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, make in addition to extrude the blend composition of the polytrimethylene terephthalate deriving from plant (PTT) resin, polybutylene terephthalate (PBT) resin, colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) and the printed layers side superimposed of the film formed and above-mentioned print film, the feed speed in the heating-up temperature 120 DEG C of crimping roller, resin molding: 20m/min, crimping pressure rolling pressure: add thermo-compressed to two films under the condition of 2.45MPa and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.
Moreover the fusion mass ratio of PTT and PBT is 4 kinds that are all set to 3:2 (PTT containing ratio=60 quality % and 51 quality %) and are all set to 4:1 (PTT containing ratio=80 quality % and 68 quality %).
< embodiment 15 >
The resin molding of embodiment 15 is set to four tunics, be formed as following resin molding: it derives from polytrimethylene terephthalate (PTT) resin of plant by comprising, the blend composition of polybutylene terephthalate (PBT) resin and colouring agent, or, the layer of the blend composition of polybutylene terephthalate (PBT) resin and colouring agent is as the 1st layer, thereon, printed layers is formed as the 2nd layer, thereon, as the 3rd layer, composite copolymerization closes PET (PET) resin bed, and then thereon, as the 4th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, comprise in layer more than at least one deck of the resin molding beyond printed layers derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 15 be utilize co-extrusion pressure using through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), lubricant (0.15 heavy amount %) blend composition, with PET (PET) resin making the M-phthalic acid 15mol% combined polymerization as sour composition, be squeezed in from T-shaped die head duplicature casting roller being made thickness 40 μm with Thickness Ratio 1:3.In the combined polymerization pet layer surface of this duplicature, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, make in addition to extrude the blend composition of the polytrimethylene terephthalate deriving from plant (PTT) resin, polybutylene terephthalate (PBT) resin, colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) and the printed layers side superimposed of the film formed and above-mentioned print film, the feed speed in the heating-up temperature 120 DEG C of crimping roller, resin molding: 20m/min, crimping pressure rolling pressure: add thermo-compressed to two films under the condition of 2.45MPa and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.Ultra-violet absorber is that use is identical with embodiment 14.
Moreover the fusion mass ratio of PTT and PBT is set to 3:2 (PTT containing ratio=51 quality %).
< embodiment 16 >
The resin molding of embodiment 16 is set to five tunics, be formed as following resin molding: it derives from polytrimethylene terephthalate (PTT) resin of plant by comprising, the blend composition layer of polybutylene terephthalate (PBT) resin and colouring agent is as the 1st layer, thereon, printed layers is formed as the 2nd layer, thereon, as the 3rd layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin, or the layer of polybutylene terephthalate (PBT) resin, thereon, as the 4th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin, or the layer of polybutylene terephthalate (PBT) resin, and then thereon, as the 5th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, comprise in layer more than at least one deck of the resin molding beyond printed layers derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 16 utilizes co-extrusion pressure by through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), the blend composition of lubricant (0.15 quality %), derive from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin, with polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and lubricant (0.15 quality %), be squeezed in from T-shaped die head trilamellar membrane casting roller being made thickness 45 μm with Thickness Ratio 1:6:2.In the layer surface not comprising ultra-violet absorber of this trilamellar membrane, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, make in addition to extrude the blend composition of the polytrimethylene terephthalate deriving from plant (PTT) resin, polybutylene terephthalate (PBT) resin, colouring agent (pigment 15 quality %) and lubricant (0.15 quality %) and the printed layers side superimposed of the film formed and above-mentioned print film, the feed speed in the heating-up temperature 120 DEG C of crimping roller, resin molding: 20m/min, crimping pressure rolling pressure: add thermo-compressed to two films under the condition of 2.45MPa and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.Ultra-violet absorber is that use is identical with embodiment 14.
Moreover the fusion mass ratio of PTT and PBT is all set to 3:2 (PTT containing ratio=60 quality % and 51 quality %).
< embodiment 17 >
The resin molding of embodiment 17 is set to five tunics, be formed as following resin molding: using the formation of the double-layer resin film described in embodiment 10 as the 1st layer and the 2nd layer, on the 2nd layer, printed layers is formed as the 3rd layer, thereon, as the 4th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin, or the layer of polybutylene terephthalate (PBT) resin, and then thereon, as the 5th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, comprise in layer more than at least one deck of the resin molding beyond printed layers derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 17 be utilize co-extrusion pressure by through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), lubricant (0.15 quality %) blend composition, with the blend composition deriving from polytrimethylene terephthalate (PTT) resin of plant, polybutylene terephthalate (PBT) resin and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 45 μm with Thickness Ratio 1:8.In the layer surface not comprising ultra-violet absorber of this duplicature, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, in addition, utilize co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %), with polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %) and lubricant (0.15 heavy amount %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 80 μm with Thickness Ratio 4:1, what make this duplicature does not contain the aspect of lubricant and the printed layers side superimposed of above-mentioned print film, in the heating-up temperature 120 DEG C of crimping roller, the feed speed of resin molding: 20m/min, crimping pressure rolling pressure: under the condition of 2.45MPa, thermo-compressed is added to two films and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.Ultra-violet absorber is that use is identical with embodiment 14.
Moreover the fusion mass ratio of PTT and PBT is 4 kinds that are set to the situation (PTT containing ratio=60 quality % and 51 quality %) being 3:2 and the situation (PTT containing ratio=80 quality % and 68 quality %) being 4:1.
< embodiment 18 >
The resin molding of embodiment 18 is set to five tunics, be formed as following resin molding: using the formation of the double-layer resin film described in embodiment 10 as the 1st layer and the 2nd layer, on the 2nd layer, printed layers is formed as the 3rd layer, thereon, as the 4th layer, composite copolymerization closes PET (PET) resin bed, and then thereon, as the 5th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, comprise in layer more than at least one deck of the resin molding beyond printed layers derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 18 be utilize co-extrusion pressure using through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), lubricant (0.15 quality %) blend composition, with PET (PET) resin making the M-phthalic acid 15mol% combined polymerization as sour composition, be squeezed in from T-shaped die head duplicature casting roller being made thickness 40 μm with Thickness Ratio 1:3.In the combined polymerization pet layer surface of this duplicature, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, in addition, utilize co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %), with polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %) and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 100 μm with Thickness Ratio 4:1, what make this duplicature does not contain the aspect of lubricant and the printed layers side superimposed of above-mentioned print film, in the heating-up temperature 120 DEG C of crimping roller, the feed speed of resin molding: 20m/min, crimping pressure rolling pressure: under the condition of 2.45MPa, thermo-compressed is added to two films and compound and make composite resin membrane.
Lubricant is that use is identical with embodiment 3.Ultra-violet absorber is that use is identical with embodiment 14.
Moreover the fusion mass ratio of PTT and PBT is 2 kinds that are set to 3:2 (PTT containing ratio=51 quality %) and 1:2 (PTT containing ratio=28.3 quality %).
< embodiment 19 >
The resin molding of embodiment 19 is set to six layers of resin molding, be formed as following resin molding: using the formation of the double-layer resin film described in embodiment 10 as the 1st layer and the 2nd layer, on the 2nd layer, printed layers is formed as the 3rd layer, thereon, polytrimethylene terephthalate (PTT) resin deriving from plant is compound in as the 4th layer, the blend composition of polybutylene terephthalate (PBT) resin, or the layer containing lubricant in polybutylene terephthalate (PBT) resin, and then thereon, as the 5th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin, or the layer of polybutylene terephthalate (PBT) resin, and then thereon, as the 6th layer, superpacket is containing polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber, or the layer of the blend composition of polybutylene terephthalate (PBT) resin and ultra-violet absorber.
Further, comprise in layer more than at least one deck of the resin molding beyond printed layers derive from plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blending resin.
The resin molding of embodiment 19 utilizes co-extrusion pressure by through polybutylene terephthalate (PBT) resin of extruder heating and melting and ultra-violet absorber (5 quality %), the blend composition of lubricant (0.15 quality %), derive from polytrimethylene terephthalate (PTT) resin of plant, the blend composition of polybutylene terephthalate (PBT) resin, with polytrimethylene terephthalate (PTT) resin deriving from plant, the blend composition of polybutylene terephthalate (PBT) resin and lubricant (0.15 quality %), be squeezed in from T-shaped die head trilamellar membrane casting roller being made thickness 45 μm with Thickness Ratio 1:6:2.In the layer surface not comprising ultra-violet absorber of this trilamellar membrane, utilize gravure rotary machine printed solid printed layers and pattern printed layers.
Thereafter, in addition, utilize co-extrusion pressure by polytrimethylene terephthalate (PTT) resin deriving from plant through extruder heating and melting, polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %), with polybutylene terephthalate (PBT) resin, the blend composition of colouring agent (pigment 15 quality %) and lubricant (0.15 quality %), be squeezed in from T-shaped die head duplicature casting roller being made thickness 80 μm with Thickness Ratio 4:1, what make this duplicature does not contain the aspect of lubricant and the printed layers side superimposed of above-mentioned print film, in the heating-up temperature 120 DEG C of crimping roller, the feed speed of resin molding: 20m/min, crimping pressure rolling pressure: under the condition of 2.45MPa, thermo-compressed is added to two films and compound and make composite resin membrane.
Ultra-violet absorber is that use is identical with embodiment 14.
Moreover the fusion mass ratio of PTT and PBT is all set to 3:2 (PTT containing ratio=60 quality % and 51 quality %).
< embodiment 20 >
The resin molding of embodiment 20 is formed as in the resin molding such as any one of above-described embodiment 4,6 to 11,18, makes 2 ~ 15 % by mole of the terephthalic acid (TPA) of the sour composition as formed combined polymerization PET (PET) resin to form through M-phthalic acid replacement.
Herein, the reason being set to 2 ~ 15 % by mole is by making terephthalic acid (TPA) replace through M-phthalic acid, and crystalloid or fusing point decline and flexibility increases, if do not reach 2%, then its effect is weak, if more than 15 % by mole, then and fusing point excessive descent and overbating.
< embodiment 21 >
The resin molding of embodiment 21 is formed as in the resin molding such as any one of above-described embodiment 12,13, replace with formed twin shaft and extend PET (BO-PET) resin, and 2 ~ 15 % by mole of twin shafts replaced through M-phthalic acid being set to the terephthalic acid (TPA) of the sour composition made as PET extend combined polymerization polyethylene terephthalate resin.
Herein, the reason being set to 2 ~ 15 % by mole is identical with the situation of embodiment 20.
< embodiment 22 >
The resin molding of embodiment 22 is formed as in the resin molding such as any one of above-described embodiment 1 to 21, comprises lubricant in the arbitrary resin bed more than formed one deck.
Lubricant is that use is identical with embodiment 3.
< embodiment 23 >
The resin molding of embodiment 23 is the layers (layer of last compound) on the most top layer be formed as the resin molding become any one of embodiment 1 to 22, and forming embossing jog by roller processing and give has relief high design.
The resin molding of embodiment 23 is the most surfaces for preformed resin molding, carries out adding hot-working and to form embossing concavo-convex under the condition of the feed speed in dandy roll temperature 120 DEG C, resin molding: 20m/min, embossing pressure: 2.45MPa.
< embodiment 24 >
The resin molding of embodiment 24 is formed as on the layer (layer of last compound) on most top layer becoming the resin molding any one of embodiment 1 to 22, forms minute surface, give the high design that minute surface arranges by roller processing.
The resin molding of embodiment 24 is the most surfaces to preformed resin molding, the feed speed in mirror roller temperature 120 DEG C, resin molding: 20m/min, processing pressure: carry out under the condition of 1MPa adding hot-working and implementing mirror finish.
< embodiment 25 >
The resin molding of embodiment 25 is formed as in the resin molding such as any one of embodiment 1 to 24, and the PTT containing ratio being blended with the resin of PBT and PTT is set to 20 ~ 80%.
In addition, PTT containing ratio is preferably and is set to 30 ~ 70%, and then is preferably and is set to 40 ~ 60%.
Namely, according to Fig. 6, when the containing ratio of PTT resin is the situation of 20 ~ 80%, spring rate display minimum at 45 DEG C, its reason is, if PTT resin containing ratio is set to 20 ~ 80%, is preferably and is set to 30 ~ 70% and then be preferably the processability be set near 40 ~ 60%, Tg and become good.
Its result, by the PTT containing ratio optimization making PBT/PTT blending resin, is namely convenient to, in the temperature province near Tg, also can reduce spring rate, can obtains the resin bed that processability is good.
< embodiment 26 >
The resin molding of embodiment 26 via solid, arbitrary resin molding in such as embodiment 1 to 25 is compound in the one side of substrate and is formed as and resin molding composite decorating board.
Herein, as solid, use polyester urethane resin system solid.
That is, in heating-up temperature: 210 DEG C, then pressure: 1.47MPa, crimping the time: under the condition of 5 seconds, on the Zinc alloy electroplating steel plate of thickness 0.5mm with 10g/m 2the base material of coating weight coated polyester urethane resin system solid carry out adding thermo-compressed, and resin molding described in compound embodiment 1 to 25, and be set to test piece.At processing temperature 45 DEG C, use squeezer to carry out bending process to this test piece, result, the good products formed of the stripping without resin molding can be obtained, the possibility being used as decorative panel can be confirmed.
Utilizability in industry
Resin molding of the present invention can be used as the resin molding using and derive from the raw material of plant, it uses the raw material deriving from plant, improve the biotic ratio of resin molding in the mode of the condition meeting biomarker, and give and the previous performance utilizing the resin molding same degree of petroleum plastic cement.
And then be adhesion, processability, excellent in te pins of durability with the decorative panel of this resin molding compound on substrate, the utilizability therefore in industry is high.

Claims (31)

1. a resin molding, is characterized in that: following resin bed A, B or C layer deriving from plant comprising more than 1 layer:
A layer: the polytrimethylene terephthalate resin deriving from plant, the polyethylene terephthalate resin deriving from plant, derive from the olefin-based resin (polypropylene, polyethylene) of plant, derive from any one or these blend compositions of more than two kinds above-mentioned of the polycarbonate resin of plant;
B layer: in derive from plant polytrimethylene terephthalate resin, derive from plant polyethylene terephthalate resin, derive from plant olefin-based resin (polypropylene, polyethylene), derive from plant polycarbonate resin any one or these blend compositions of more than two kinds above-mentioned in add and derive from the compatilizer of plant and/or derive from the elastomer of plant;
C layer: in derive from plant polytrimethylene terephthalate resin, derive from plant polyethylene terephthalate resin, derive from plant olefin-based resin (polypropylene, polyethylene), derive from plant polycarbonate resin any one or these blend compositions of more than two kinds above-mentioned in add the ionomer deriving from plant.
2. a resin molding, it is characterized in that compound more than 1 layer according to claim 1 derive from plant resin bed A, B or C layer and as the following D layer on top layer or E layer:
D layer: the crystalloid mylar of any one or these blend compositions of more than two kinds above-mentioned comprising polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyethylene terephthalate resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin;
E layer: the substantive noncrystalline polyester of any one or these blend compositions of more than two kinds above-mentioned comprising combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, polycarbonate resin.
3. a resin molding, is characterized in that according to claim 1 resin bed A, B or C layer that derive from plant of more than 1 layer of compound as intermediate layer; And as the D layer of most top layer and undermost claim 2 or E layer.
4. a resin molding, is characterized in that, alternately compound is according to claim 1 derives from resin bed A, B or C layer of plant and the D layer of claim 2 or E layer for it, and above-mentioned D layer or E layer are most top layer and orlop.
5. a resin molding, it is characterized in that via or not via solid compound more than 2 layers according to described resin molding arbitrary in Claims 1-4.
6. according to described resin molding arbitrary in claim 1 to 5, wherein in the above-mentioned resin bed A deriving from plant, be blended with the composition forming D layer in B or C layer and (comprise polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyethylene terephthalate resin, combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, any one of combined polymerization polytrimethylene terephthalate resin, or the crystalloid polyester of these blend compositions of more than two kinds above-mentioned), or the composition forming E layer (comprises combined polymerization polyethylene terephthalate resin, combined polymerization polybutylene terephthalate resin, combined polymerization polytrimethylene terephthalate resin, any one of polycarbonate resin, or the substantive noncrystalline polyester of these blend compositions of more than two kinds above-mentioned).
7. a resin molding, is characterized in that, between according to any layer of described resin molding arbitrary in claim 1 to 6, arrange printed layers.
8. a single-layer resin film, is characterized in that comprising the blend composition of polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent deriving from plant.
9. a single-layer resin film, is characterized in that comprising: the blend composition of polybutylene terephthalate resin, the polytrimethylene terephthalate resin deriving from plant, combined polymerization polyethylene terephthalate resin and colouring agent; Or derive from the blend composition of the polytrimethylene terephthalate resin of plant, combined polymerization polyethylene terephthalate resin and colouring agent.
10. a double-layer resin film, is characterized in that: using the layer of the blend composition of the blend composition or polybutylene terephthalate resin and colouring agent that comprise the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of colouring agent or the blend composition of polybutylene terephthalate resin and colouring agent;
The polytrimethylene terephthalate resin and polybutylene terephthalate resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer or the 2nd layer resin molding.
11. 1 kinds of double-layer resin films, is characterized in that: using the layer of the blend composition of the blend composition or polybutylene terephthalate resin and colouring agent that comprise the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, as the 2nd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate resin, combined polymerization polyethylene terephthalate resin and colouring agent or the blend composition of polybutylene terephthalate resin, the polytrimethylene terephthalate resin deriving from plant, combined polymerization polyethylene terephthalate resin and colouring agent;
The polytrimethylene terephthalate resin and polybutylene terephthalate resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer or the 2nd layer resin molding.
12. 1 kinds of double-layer resin films, is characterized in that: will comprise the layer of combined polymerization polyethylene terephthalate resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the blend composition of the polytrimethylene terephthalate resin and colouring agent that derive from plant or in deriving from the blend composition of the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and colouring agent and then being blended with the layer of resin combination of antistatic agent.
13. 1 kinds of double-layer resin films, is characterized in that: will comprise the layer of combined polymerization polyethylene terephthalate resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer of blend composition deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and colouring agent.
14. 1 kinds of three-layer resin films, is characterized in that: using the formation of double-layer resin film according to claim 10 as the 1st layer and the 2nd layer;
On the 2nd layer, as the 3rd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate resin, combined polymerization polyethylene terephthalate resin and colouring agent or the blend composition of polybutylene terephthalate resin, the polytrimethylene terephthalate resin deriving from plant, combined polymerization polyethylene terephthalate resin and colouring agent;
The polytrimethylene terephthalate resin and polybutylene terephthalate resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer ~ the 3rd layer of resin molding.
15. 1 kinds of three-layer resin films, is characterized in that: will comprise the layer of combined polymerization polyethylene terephthalate resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of colouring agent or the blend composition of polybutylene terephthalate resin and colouring agent;
Thereon, as the 3rd layer superpacket containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin, colouring agent and the blend composition of antistatic agent or the blend composition of polybutylene terephthalate resin, colouring agent and antistatic agent;
The polytrimethylene terephthalate resin and polybutylene terephthalate resin that derive from plant is blended with in layer more than at least one deck of above-mentioned 1st layer ~ the 3rd layer of resin molding.
16. 1 kinds of three-layer resin films, is characterized in that: will comprise the layer of combined polymerization polyethylene terephthalate resin as the 1st layer;
Thereon, as the 2nd layer superpacket containing the layer of blend composition deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and colouring agent;
Thereon, as the 3rd layer, superpacket contains the layer of the blend composition of polybutylene terephthalate resin and colouring agent.
17. 1 kinds of three-layer resin films, is characterized in that: will comprise the blend composition layer of the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer, superpacket extends the layer of polyethylene terephthalate resin containing twin shaft.
18. 1 kinds of four layers of resin moldings, is characterized in that: using the formation of double-layer resin film according to claim 10 as the 1st layer and the 2nd layer;
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer, compound twin shaft extends polyethylene terephthalate resin.
19. 1 kinds of four layers of resin moldings, is characterized in that: using the layer of the blend composition of the blend composition or polybutylene terephthalate resin and colouring agent that comprise the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer superpacket containing deriving from the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
And then thereon, as the 4th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
20. 1 kinds of four layers of resin moldings, is characterized in that: using the layer of the blend composition of the blend composition or polybutylene terephthalate resin and colouring agent that comprise the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer, composite copolymerization closes polyethylene terephthalate resin layer;
And then thereon, as the 4th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
21. 1 kinds of five layers of resin moldings, is characterized in that: using the layer of the blend composition of the blend composition or polybutylene terephthalate resin and colouring agent that comprise the polytrimethylene terephthalate resin, polybutylene terephthalate resin and the colouring agent that derive from plant as the 1st layer;
Thereon, printed layers is formed with as the 2nd layer;
Thereon, as the 3rd layer superpacket containing deriving from the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
Thereon, as the 4th layer superpacket containing deriving from the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
22. 1 kinds of five layers of resin moldings, is characterized in that: using the formation of double-layer resin film according to claim 10 as the 1st layer and the 2nd layer;
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer superpacket containing deriving from the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
23. 1 kinds of five layers of resin moldings, is characterized in that: using the formation of double-layer resin film according to claim 10 as the 1st layer and the 2nd layer;
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer, composite copolymerization closes polyethylene terephthalate resin layer;
And then thereon, as the 5th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
24. 1 kinds of six layers of resin moldings, is characterized in that: using the formation of double-layer resin film according to claim 10 as the 1st layer and the 2nd layer;
On the 2nd layer, be formed with printed layers as the 3rd layer;
Thereon, as the 4th layer complex source in the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
And then thereon, as the 5th layer, superpacket is containing deriving from the polytrimethylene terephthalate resin of plant, the blend composition of polybutylene terephthalate resin or the layer of polybutylene terephthalate resin;
And then thereon, as the 6th layer, superpacket is containing the layer deriving from the polytrimethylene terephthalate resin of plant, polybutylene terephthalate resin and the blend composition of ultra-violet absorber or the blend composition of polybutylene terephthalate resin and ultra-violet absorber;
The polytrimethylene terephthalate resin deriving from plant and polybutylene terephthalate resin is blended with in layer more than at least one deck of the resin molding beyond above-mentioned printed layers.
25. according to described resin molding arbitrary in claim 9,11 to 16,23, is make 2 ~ 15 % by mole of the terephthalic acid (TPA) of the sour composition as formed combined polymerization polyethylene terephthalate resin to form through M-phthalic acid replacement.
26. according to described resin molding arbitrary in claim 17,18, wherein replace with formed twin shaft and extend polyethylene terephthalate resin, and 2 ~ 15 % by mole of twin shafts replaced through M-phthalic acid being set to the terephthalic acid (TPA) of the sour composition made as PET extend combined polymerization polyethylene terephthalate resin.
27., according to described resin molding arbitrary in claim 1 to 26, comprise lubricant in the arbitrary resin bed wherein more than formed one deck.
28. 1 kinds of resin moldings, is characterized in that: be formed with embossing jog in becoming according on the layer on the most top layer of described resin molding arbitrary in claim 1 to 27.
29. 1 kinds of resin moldings, is characterized in that: be formed with minute surface in becoming according on the layer on the most top layer of described resin molding arbitrary in claim 1 to 27.
The PTT containing ratio being blended with the resin of PBT and PTT, according to described resin molding arbitrary in claim 2 to 29, is wherein set to 20 ~ 80% by 30..
31. 1 kinds of resin molding composite decorating boards, is characterized in that: via or not via solid at least one side of substrate with according to described resin molding compound arbitrary in claims 1 to 30.
CN201380063169.5A 2012-10-26 2013-10-24 Resin film and resin film composite decorating board Active CN104837626B (en)

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